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Pompei Scavi is on the Circumvesuviana rail line, NOT on the Trenitalia rail line. From SALERNO to Pompei, you'll be alighting at the Trenitalia Pompei Station, which is a good 20-minute walk from the ruins. From SORRENTO to Pompei, you'll be alighting at the Pompei Scavi Station, which is across the street from the site entrance. From NAPLES to Pompei, it depends whether you take the Circumvesuviana train or the Trenitalia train!!!

There is another Pompei train station on a different Circumvesuviana line than the one between Naples/Sorrento, but getting there might be a process. I think this Pompei station is perhaps a bit closer than the Trenitalia Pompei station. It would require taking Trenitalia to Sarno although I don't think this train runs early(travel time 15 minutes), changing to Circumvesuviana to Poggiomarino (about 10 minutes), changing to Pompei (about 10 minutes).

If you select Pompei on the stations choices on this link (not Pompeii Scavi) and then click on open by map detail. You will see the station blinking on the map. This train makes a somewhat circular route from Naples. There are more train lines on Circumvesuviana than just Naples/Sorrento.http://www.vesuviana.it/web/en/infostazione

If you use Google maps, you will see this station just east of the ruins, the Trenitalia station just south/south east and the Pompeii Scavi station just west. Mouse over and you will see both stations showing as Pompei and the Scavi station as Villa dei Misteri.

The scavi website also lists this station (although it lists it as Pompei Santuario) and tells you which entrance to use. It also list two CSTP bus options from Salerno which may be better than the trains or Sita bus.